403 V T T P U B L I C A T I O N S

VTT PUBLICATIONS 403

Considering that there is a common need among chemical engineers to find
environmentally benign solvents, the use of relatively inexpensive carbon Antero Laitinen
dioxide solvent should increase in the future, provided that carbon dioxide
proves to be a technically feasible and economically competitive solvent in
selected industrial applications. This thesis concentrates on the extraction
of organic compounds from solid and liquid matrices using supercritical
Supercritical fluid extraction of
carbon dioxide as a solvent.
Carbon dioxide is a very good solvent for the cyclic amide, 6- organic compounds from solids
caprolactam. Carbon dioxide can potentially be used to dissolve and extract
6-caprolactam from solid and liquid matrices. The remediation of and aqueous solutions
contaminated soil by carbon dioxide extraction was studied by extracting

Supercritical fluid extraction of organic compounds from solids and aqueous solutions
selected pollutants such as polycyclic aromatic hydrocarbons and
chlorophenols from soil samples. A novel mechanically agitated
countercurrent continuous extraction column was introduced by extracting
ethanol and 1-butanol from aqueous solutions in the rotating disk column
and in the Oldshue-Rushton column.

Tt julkaisua myy Denna publikation sljs av This publication is available from

Antero Laitinen
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ISSN 12350621 (soft back ed.) ISSN 14550849 (URL: http://www.inf.vtt.fi/pdf/) TECHNICAL RESEARCH CENTRE OF FINLAND ESPOO 1999
 VTT PUBLICATIONS 403

Supercritical fluid extraction of

organic compounds from solids and
aqueous solutions

Antero Laitinen
VTT Chemical Technology
Laboratory of Chemical Engineering and Plant Design
Department of Chemical Technology
Helsinki University of Technology

Dissertation for the degree of Doctor of Technology to be

presented with due permission for public examination and debate
in Auditorium Ke 2 at Helsinki University of Technology (Espoo,
Finland) on the 21st of January, 2000, at 12 oclock noon.

TECHNICAL RESEARCH CENTRE OF FINLAND

ESPOO 1999
ISBN 9513855511 (soft back ed.)
ISSN 12350621 (soft back ed.)

ISBN 951385552-X (URL: http://www.inf.vtt.fi/pdf/)

ISSN 14550849 (URL: http://www.inf.vtt.fi/pdf/)

Copyright Valtion teknillinen tutkimuskeskus (VTT) 1999

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Technical editing Leena Ukskoski

Libella Painopalvelu Oy, Espoo 1999

Laitinen, Antero. Supercritical fluid extraction of organic compounds from solids and aqueous
solutions. Espoo 1999. Technical Research Centre of Finland, VTT Publications 403. 58 p. + app.
84 p.
Keywords organic compounds, extraction, solids, aqueous solutions, supercritical gases,
supercritical fluids, carbon dioxide, amides, lactams, solubility

Abstract
In this thesis, the extraction of organic compounds from solid and liquid
matrices using supercritical carbon dioxide as a solvent was studied.

Dense carbon dioxide is a very good solvent for the cyclic amide, 6-caprolactam.
6-caprolactam exhibits relatively high solubilities, i.e. up to around 17 wt% at
ambient temperatures, and at pressures below 220 bar. Carbon dioxide can be
used to dissolve and extract 6-caprolactam from solid and liquid matrices.

The remediation of contaminated soil by carbon dioxide extraction was studied.

The effect of extraction pressure, temperature, soil moisture content, pH, carbon
dioxide mass flow rate, and extraction time on the residual pollutant
concentration in the soil after extraction was systematically studied. The selected
pollutants were phenanthrene, 2,3,4,6-tetrachlorophenol and pentachlorophenol.
The results indicate that at least 8090 % of the initial amount of pollutant can
be removed at moderate temperatures even in the most difficult cases, and in
many cases over 99 % of the initial amount of pollutant can be removed from the
soil. Supercritical extraction is best suited to sand or silt type soils, which have a
low adsorption capacity. The extraction results are found to be case-dependent,
and soil remediation at moderate temperatures is observed to be difficult if the
pollutant binds strongly to the soil or if the acceptable level of residual
concentration is very low.

A novel mechanically agitated countercurrent continuous extraction column was

introduced by extracting ethanol and 1-butanol from aqueous solutions in the
rotating disk column and in the Oldshue-Rushton column. Column efficiencies
were measured as a function of solvent-to-feed ratio and rotor speed. Generally,
the values of the height equivalent to a theoretical stage HETS were in the range
of 0.40.8 m. Mechanical agitation enhanced the extraction only at relatively

3
high solvent-to-feed ratios. Column capacities for both types of column were
measured, and the total throughput calculated as the feed plus solvent flow rate
divided by the smallest cross-sectional area was 5080 m3h-1m-2. A mechanically
agitated column successfully combines the high capacity of supercritical spray
columns and the high efficiency of supercritical packed columns.

4
 Preface
The research described in this thesis was carried out at the Chemical laboratory
of the Technical Research Centre of Finland (VTT) during the years 19931998.
I would like to thank VTT Chemical Technology for the excellent working
facilities and for providing me with the opportunity to test my ideas. Financial
assistance from Tekes is gratefully acknowledged.

I am very grateful to Research Director Markku Auer and Professor Veikko

Komppa for providing me with the opportunity to work in this intriguing field of
research. I also want to thank my group leader, Olli Aaltonen, for his support,
interest and encouragement during this work. I greatly appreciate my supervisor,
Professor Markku Hurme, for his guidance during the course of this work. I
thank Managing Director Antti Raitakari from Chematur Ecoplanning Co. for
allowing me to publish part of the results obtained during the EUREKA-project.

I warmly thank my friends and colleagues at VTT for helping me in so many

ways during the project and for creating such a good working atmosphere. In
particular, I would like to thank my co-authors, Matti Jntti and Juha Kaunisto,
and my colleagues, Martti Alkio and Markku Rantakyl, for their support and
advices. My sincere appreciation is due to Mr. Richard Walker for revising the
language of this thesis.

My most sincere thanks are due to my parents, my sister and my brother, and
my friends for their unselfish support during this work.

Espoo, February 3rd, 1999

Antero Laitinen

5
 List of publications
The thesis is based on the following publications, which are referred to by
Roman numerals:

Laitinen, A., Jntti, M. Solubility of 6-Caprolactam in

Supercritical Carbon Dioxide. J. Chem. Eng. Data, 41(1996), pp.
14181420.

Laitinen, A., Michaux, A., Aaltonen O. Soil Cleaning by Carbon

Dioxide Extraction: A Review. Environ. Tech., 15(1994), pp.
715727.

Laitinen, A. Soil Cleaning by Carbon Dioxide Extraction. In:

Advances in Environmental Control Technology, Ecological
Issues and Environmental Impact assessment. P. N.
Cheremisinoff, (ed.). Gulf Publishing Co., Houston, Texas, 1997.
Pp. 217236.

V Laitinen, A. Remediation of Contaminated Soil by Carbon

Dioxide Extraction. Plant Design Report Series, No. 53, Helsinki
University of Technology, Espoo 1999. 20 p.

V Laitinen, A., Kaunisto, J. Hydrodynamics and Mass Transfer in a

Rotating Disk Supercritical Extraction Column. Ind. Eng. Chem.
Res., 37(1998), pp. 25292534.

V Laitinen, A., Kaunisto, J. Oldshue-Rushton Column in

Supercritical Fluid Extraction. Sep. Sci. Tech., 34(1999), pp.
18591872.

V Laitinen, A., Kaunisto, J. Supercritical Fluid Extraction of 1-

Butanol from Aqueous Solutions. J. Supercritical Fluids.,
15(1999), pp. 245252.

6
 The author' s contribution
The author has had an active role in all stages of the work reported in this
thesis, including the design and construction of the experimental
equipment, experimental design, the development of the working
procedures, the carrying out of the experiments reported in publications,
the interpretation the results, and the writing of the papers.

Matti Jntti did the modeling work in Paper . Olli Aaltonen contributed
significantly to the writing of Paper . The work of Martti Alkio in
designing and constructing the apparatus used in the soil extraction
experiments is acknowledged. A lot of the practical work in Papers V, VI
and VII was carried out by Juha Kaunisto.

7
 Contents

Abstract .................................................................................................................3

Preface...................................................................................................................5

List of publications................................................................................................6

The authors contribution ......................................................................................7

Abbreviations ......................................................................................................10

1. Introduction...................................................................................................11

2. Supercritical fluids ........................................................................................13

3. Applications of supercritical fluid extraction................................................17

3.1 Historical background ..............................................................................17
3.2 Food processing applications ...................................................................18
3.3 Reactions in supercritical media ..............................................................19
3.4 Particle production ...................................................................................20
3.5 Environmental applications......................................................................21
3.6 Separations in continuously operated columns ........................................22

4. Solubility measurements ...............................................................................24

4.1 Experimental ............................................................................................24
4.2. Solubility results .....................................................................................25

5. Soil extraction measurements .......................................................................28

5.1 Experimental ............................................................................................28
5.1.1 Soil characterization and preparation..............................................28
5.1.2 Soil extraction apparatus and procedure .........................................29
5.2. Soil extraction results.............................................................................30
5.2.1 Extraction from spiked soil .............................................................31
5.2.2 Extraction from contaminated soil..................................................33

6. Continuous column extractions.....................................................................36

6.1 Experimental ............................................................................................36
6.1.1. Equipment ......................................................................................36

8
 6.1.2 Column extraction procedure..........................................................38
6.1.3 Calculation of column efficiency....................................................39
6.2 Column extraction results ........................................................................41
6.2.1 Column efficiency...........................................................................41
6.2.2 Column capacity .............................................................................46

7. Concluding remarks ......................................................................................49

References ...........................................................................................................51

Papers IVII

Appendices of this publication are not included in the PDF version.

Please order the printed version to get the complete publication
(http://www.inf.vtt.fi/pdf/publications/1999/)

9
 Abbreviations
a interfacial area, m2/m3
C pollutant concentration in the soil, mg/kg
D column diameter, m
E extraction coefficient = mS/F
F flow rate of feed, kg/h
h holdup
HETS height equivalent to a theoretical stage, m
HTUod height of a transfer unit based on the dispersed phase, m
Kod overall mass transfer coefficient based on the dispersed phase, 1/s
m distribution coefficient (concentration in solvent phase/concentration
in feed phase)
NTUod number of transfer units based on the dispersed phase
p pressure, bar
S flow rate of the solvent, kg/h
t extraction time, min
T temperature, C
y weight fraction of solute in the dispersed phase, mole fraction in section 4
V superficial velocity, m/s
w water content in the soil, wt%
Vs slip velocity, m/s
Z total agitated height of the column, m
density, g/ml

Subscripts

1 at the top of the column

2 at the bottom of the column
c critical value, continuous phase in section 6
d dispersed phase
f final
i initial

Superscripts

* equilibrium value
through smallest cross-sectional area

10
 1. Introduction
In recent years, the use of supercritical fluid extraction for the removal of
organic compounds from different liquid and solid matrices has attracted much
attention. This technique has some advantages over more conventional
separation techniques, largely due to the unique physical properties of
supercritical fluids. Supercritical fluids exhibit a liquid-like density, while their
viscosity and diffusivity remain between gas-like and liquid-like values. Also,
the recovery of a supercritical solvent after extraction can be carried out
relatively simply by reducing the pressure and evaporating the solvent, because a
supercritical solvent is usually a gas at NTP. There are several applications in
the food processing, pharmaceutical and chemical industries, notably in the
decaffeination of coffee beans and the production of polyethylene [1].

Another application now under development is the clean-up of contaminated soil

and hazardous waste sites. Incineration, washing, biodegradation, isolation,
solidification and solvent extraction are potential methods for the remediation of
contaminated soil. In solvent extraction treatment technologies, the
contaminated soil is first mixed with a suitable solvent. The contaminant
dissolves into the solvent and is thereby removed from the cleaned soil. The
spent solvent is then evaporated to get the contaminant into a very concentrated
form. The isolated contaminant is transferred to an appropriate end treatment,
such as an incineration plant, or, if the contaminant is valuable, a recovery
process. The pure solvent that is evaporated from the spent extraction solution is
recycled back to the soil extraction apparatus. Conventional extraction or
leaching processes use organic, liquid solvents as the extraction medium.

In general, distillation is used in the chemical industry to separate organic

products or wastes from concentrated aqueous solutions. However, the
distillation of dilute aqueous solutions is energy intensive, and the formation of
azeotropes can prevent the use of ordinary distillation. Other separation
techniques, such as liquid-liquid extraction, could provide an appropriate
solution if ordinary distillation is not applicable. In ternary liquid-liquid
extraction, a liquid feed consisting of a carrier and solute is contacted with a
solvent, which is practically immiscible with the carrier, but at the same time, a
good solvent for the solute. Thus, the solute is transferred from the carrier to the
solvent. The solute can be separated from the solvent by, for example,

11
distillation; the solvent is then recycled. Extraction processes are applied in the
petroleum industry to separate close-boiling hydrocarbon mixtures (e.g. the BTX
-process), in the pharmaceutical industry to separate heat-sensitive antibiotics,
and in the chemical industry to separate, for example, caprolactam from aqueous
feed. Supercritical fluids have been tested as solvents in several extraction
applications, such as the extraction of ethanol or acetic acid from aqueous
solutions [1].

This thesis focuses on the supercritical fluid extraction of organic compounds

from solids and aqueous solutions. The aim of this work is to study the
engineering fundamentals, which would allow the technically and economically
successful exploitation of supercritical extraction technology to solve the
practical separation problems

Before successful supercritical extraction operations can be started, it is

necessary to understand the solvent behavior of compressed gases. Therefore,
firstly, the solubility of 6-caprolactam was measured and the Peng-Robinson
equation of state was used to model the solubility of 6-caprolactam in
supercritical carbon dioxide [I]. Secondly, the possibility of using the
compressed carbon dioxide at a supercritical state instead of a liquid solvent to
extract organic compounds from contaminated soils was studied [IIIV].
Selected organic compounds including polycyclic aromatic hydrocarbons
(PAHs) and chlorophenols were extracted from spiked and real contaminated
samples. Thirdly, a high-pressure mechanically agitated continuous
countercurrent extraction column was introduced, and the extraction of ethanol
and 1-butanol from aqueous solutions in this column was studied [VVII].

12
 2. Supercritical fluids
A substance is at the supercritical state, i.e.a supercritical fluid, when its
temperature and pressure are simultaneously higher than the critical values. A
supercritical fluid exists in a single fluid phase possessing characteristics
between those of gases and liquids. Figure 1 illustrates a pressure-temperature
diagram in the critical region of pure carbon dioxide.

Figure 1. The phase diagram of carbon dioxide.

Above the critical temperature a liquid phase will not appear regardless of how
much the pressure is increased. The critical pressure is the pressure, which
causes the gas to become a liquid at the critical temperature. The density of a
compound at the critical point is called the critical density. The critical
temperatures, pressures and densities of some common solvents are listed in
Table 1.

13
Table 1. Critical properties of selected solvents [1, 3].

Tc pc c
SOLVENT (C) (bar) (g /ml)
Ammonia 132.5 113.5 0.24
Benzene 289.0 48.9 0.30
n-Butane 152.0 38.0 0.23
Carbon dioxide 31.1 73.8 0.45
Chlorotrifluoromethane 28.8 39.5 0.58
Dichlorodifluoromethane 111.7 39.9 0.56
Ethane 32.2 48.9 0.20
Ethanol 243.4 63.8 0.28
Ethylene 9.3 50.4 0.22
Isopropanol 235.3 47.6 0.27
Methanol 240.5 79.9 0.27
Nitrous oxide 36.5 72.3 0.46
n-Propane 96.8 42.6 0.22
Propylene 91.9 46.2 0.23
Toluene 318.6 41.1 0.29
Water 374.2 221.2 0.34

The compressibility of a supercritical fluid just above the critical temperature is

large compared to the compressibility of ordinary liquids. A small change in the
pressure or temperature of a supercritical fluid generally causes a large change in
its density. A commonly accepted opinion is that the solvent power of a
supercritical fluid is mainly related to its density in the critical point region [2].
A high density generally implies a strong solvating capacity. The unique
property of a supercritical fluid is, that its solvating power can be tuned by
changing either its temperature or pressure.

A significant cost factor for many conventional liquid-liquid extraction

processes is the recovery of the spent extraction solvent. The separation of the
solvent from the solute is usually done by distillation, which can sometimes be
very energy-consuming. If a supercritical solvent is applied, the solute can be
separated from the mixture by e.g. lowering the pressure of the mixture. One

14
should remember, that to recycle the supercritical solvent, it must be compressed
again. This can be a significant cost factor, if the difference between the pressure
in the extraction vessel and the pressure in the separator is relatively large.

Even though the density of a supercritical fluid increases with pressure and
becomes liquid-like, the viscosity and diffusivity remain between liquid-like and
gas-like values [4]. Additionally, supercritical fluids exhibit almost zero surface
tension, which allows facile penetration into microporous materials. As a result
of the advantageous combination of physicochemical properties, the extraction
process can often be carried out more efficiently with a supercritical solvent than
it can with an organic liquid one. A comparison of selected physicochemical
properties of liquids, gases and supercritical fluids is presented in Table 2.

Table 2. Selected physicochemical properties of liquids, gases and supercritical

fluids [1].

Properties Liquid Supercritical fluid Gas

Density (kg/m3) 1 000 200800 1

Viscosity (mPas) 0.51.0 0.050.1 0.01

Diffusivity (cm2/s) 10-5 10-410-3 0.1

The critical temperature (Tc) of the compound depends on the polarity of the
compound. As seen in Table 1, the critical temperatures of non-polar gases, such
as carbon dioxide or ethane, are below 50 C, whereas for polar compounds,
such as methanol or water, the critical temperature is well above 200 C. In
practice, especially in food-related industries, it is usually desirable that the
critical temperature of the solvent is below 100 C. Therefore, the solvents
commonly used for supercritical operations are low molecular weight gases,
such as carbon dioxide, ethane and propane.

Carbon dioxide is the most commonly used solvent in industrial practice for
several reasons. Carbon dioxide has a technically convenient critical pressure
and temperature of 73.8 bar and 31.1 C, respectively. It is non-toxic, non-

15
flammable, non-reactive, non-corrosive, and abundant. Furthermore, it is the
second least expensive solvent after water [5], and it does not leave any solvent
residue after extraction.

Carbon dioxide is a relatively good solvent for hydrocarbons and non-polar

solids. However, owing to the unique properties of supercritical solvents and to
the rather large quadrupole moment of carbon dioxide in particular, supercritical
carbon dioxide will dissolve many relatively volatile polar compounds. This
explains why methanol and DMSO, for example, are miscible with supercritical
carbon dioxide at 400 bar and 40 C [1]. Adding small amounts of polar co-
solvents, called entrainers, to the bulk carbon dioxide can enhance the solubility
of polar, non-volatile solutes in supercritical carbon dioxide. Water and short-
chain alcohols are efficient and usually the most acceptable co-solvents in
industrial practice. Only the organic, non-polar or volatile compounds are
expected to be effectively extracted from soils and aqueous matrices. An
excellent review of solid solubilities in supercritical carbon dioxide is offered by
Bartle et al. [6].

16
 3. Applications of supercritical fluid
extraction
3.1 Historical background

In 1879 Hannay and Hogard [7] reported that changes in pressure caused
inorganic salts like cobalt chloride to dissolve in or precipitate from ethanol at a
temperature above the critical temperature of ethanol. Later, Villard [8]
demonstrated that gases such as methane, ethylene, carbon dioxide and nitrous
oxide dissolve a number of liquid or solid compounds, such as camphor, stearic
acid or paraffin wax. Since then, several authors have described the ability of a
supercritical fluid to dissolve solid materials. The solubility of napthalene in
supercritical ethylene was studied by Diepen and Scheffer in 1948 [9], followed
by several other studies [1015] in which the solubility of napthalene in a variety
of supercritical solvents was examined. In 1954 Francis [16] presented a study,
where he reported phase diagrams for 464 ternary systems containing liquid
carbon dioxide, and measured the solubility of 261 organic compounds in near
critical liquid carbon dioxide. Even though supercritical carbon dioxide was not
applied in the study, the data can be used to assess the solvent power of
supercritical carbon dioxide, because a compound which is soluble in liquid
carbon dioxide is usually also soluble in supercritical carbon dioxide.

The ability of near critical or supercritical solvents to dissolve organic

compounds was utilized in industrial operations in the middle of the twentieth
century. A process for deasphalting lube oils using subcritical propane
introduced by Wilson et al. [17] in 1936 is still used today. This process takes
advantage of the possibility of changing the density of propane in the vicinity of
its critical point. Since the solvent characteristics of propane can be changed
dramatically by changing the pressure or temperature, this single solvent can be
used to separate various fractions, including paraffin wax, asphalt, heavy ends,
naphthalenes, color bodies, and purified light oil. The Solexol Process developed
by Dickinson and Meyers [18] for the separation and purification of vegetable
and fish oils uses propane as a solvent. The purpose of this process is to
concentrate the polyunsaturated triglycerides and to extract vitamin A from the
fish oils. The commercialized ROSE Process (Residuum Oil Supercritical
Extraction) uses subcritical butane or pentane to fractionate residuum oil [19].

17
 3.2 Food processing applications

Food processing is the most widely investigated industrial application of

supercritical fluid technology. Carbon dioxide is a particularly suitable solvent
for food processing applications, because its moderate critical temperature (TC =
31.1 C) enables the extraction of thermally labile food compounds.
Additionally, it is non-toxic, environmentally acceptable, and relatively
inexpensive. Compared with conventional solvents such as hexane, carbon
dioxide does not leave any harmful solvent residue after extraction. The food
material to be extracted is often solid, and therefore semi-batch extraction is
frequently used. A schematic picture of a semi-batch supercritical fluid
extraction system is presented in Figure 2.

Figure 2. Operating principle of a semi-batch supercritical fluid extraction

system.

Liquid carbon dioxide from the container is pressurized by the pump and heated
to the extraction temperature by the heat exchanger. Pressurized carbon dioxide
flows through the extraction vessel and dissolves the soluble extract. Carbon
dioxide loaded with the extract is then flashed in the pressure release valve and
carbon dioxide, now in the vapor and liquid phase, flows into the separator,
where the liquid fraction is vaporized by heating. The extract is not soluble in

18
carbon dioxide vapor and can be removed from the bottom of the separator.
Carbon dioxide vapor is condensed and returned to the container. A heat pump
system can be installed to transfer heat from the condenser to the separator.

Supercritical carbon dioxide is industrially used to extract caffeine from green

moist coffee beans and to produce pharmaceuticals, natural products, and specialty
chemicals. The largest plants use batch extraction vessels with volumes up to tens
of cubic meters. The flow rate of carbon dioxide in the largest plants are several
tons per hour and the operating pressures are usually within 200300 bars.
Recently, Maxwell House Division of General Foods employed a 25 000 000 kg/a
coffee decaffeination supercritical extraction process in Houston [1]. The semi-
continuous high pressure extraction column is estimated to be around 23 m high.

3.3 Reactions in supercritical media

Polyethylene can be produced by polymerizing supercritical ethylene. In the case

of radical polymerization, an ethylene pressure of 1 2003 000 bar is required at
150300 C to produce polyethylene with a sufficient high molecular weight.
Oxygen or organic peroxides are used as initiators [20]. The fact that the solvent
power of a supercritical fluid can be changed by changing its pressure can be
utilized to fractionate polymers such as polyethylene, ethylene-based
copolymers, and polysiloxane [1]. In principle, the synthetic polymer can first be
dissolved in a supercritical fluid solvent at high pressure. The pressure is then
slightly reduced in a pressure reduction valve. Because the density of the
supercritical fluid is also reduced, the highest molecular weight polymer
fraction is no longer soluble in the solvent. This fraction is precipites into the
separator vessel. The pressure of the mixture which leaves the first separation
vessel is then reduced again, causing the next highest molecular weight polymer
fraction to precipitate.

Supercritical fluids serve as a reaction medium for the reactants, catalysts and
products, or they can be a solvent and a reactant at the same time, as in
polyethylene-free radical polymerization. Additionally, the properties of
supercritical fluids may be utilized to separate the product from the reactants or
catalyst by reducing the pressure of the reaction mixture. In the mid 1980s it was

19
discovered that enzymes are active in supercritical carbon dioxide [21, 22].
Since then, several supercritical fluid research groups have investigated
enzymatic reactions, and more than 200 papers have been published. The basic
motivation is to replace the hazardous organic solvents with environmentally
acceptable carbon dioxide. Also, enzymes are more stable in the non-aqueous
supercritical reaction environment than in the conventional aqueous
environment. Review articles concerning enzymatic catalysis in supercritical
fluids are available [2325].

Supercritical water oxidation introduced by Modell [26] is used to destroy

organic wastes. This technique benefits from the fact that supercritical water (TC
= 374 C, pC = 221 bar) behaves like a non-polar solvent, showing complete
miscibility for organics like toluene and for gases like oxygen and hydrogen.
Under supercritical conditions (T > 374 C) organics such as chlorinated
hydrocarbons are quickly oxidized into carbon monoxide, water and
hydrochloric acid. Corrosion can be a severe problem in supercritical water
oxidation reactors, especially if halogen-containing organics are oxidized.
Furthermore, supercritical water does not dissolve salts, and depositions of salts
can block the pipes and valves.

Several other reactions, such as oxygenation [27], hydroformulation [28],

alkylation [29] and hydrogenation [30, 31] have been studied in supercritical
fluids. Hydrogenation is a particularly interesting application. Supercritical
fluids are almost completely miscible with hydrogen gas. This property means
that hydrogenation rates in supercritical media are presumably much faster than
in the conventional liquid-phase hydrogenations because of the high hydrogen
concentration in the reaction mixture and on the catalyst surface. By applying a
supercritical solvent, the external mass transfer resistance can be neglected.

3.4 Particle production

Supercritical fluids can be used as particle formation media [32, 33]. Two
techniques have been used to make particles from supercritical fluids. Rapid
expansion from supercritical solutions (RESS) is used to form fine particles of
substances which are soluble in a supercritical solvent. In the RESS technique
the substance is first dissolved in a supercritical solvent, after which the pressure

20
is rapidly decreased in a specifically designed nozzle, resulting in
supersaturation of the substance in the supercritical solvent and leading to the
formation of small particles with a narrow particle size distribution. Gas anti-
solvent recrystallization (GAS) is used for substances, which are not soluble in a
supercritical solvent. The substance is dissolved in a liquid solvent such as
methanol, and a supercritical solvent acts as an anti-solvent to rapidly precipitate
the substance in a nozzle.

3.5 Environmental applications

The remediation of contaminated soil by carbon dioxide extraction is considered

to be a promising technique, and it has received a great deal of interest over the
past ten years. Several authors [3440] have extracted on a bench scale PAHs
such as naphthalene, fluoranthene, pyrene, benzo[a]-anthracene, benzo[a]-
pyrene and perylene, diesel oil containing C13-C22 hydrocarbons, PCBs,
chlorophenols such as 2-chlorophenol and 2,4,6-trichlorophenol, and dioxins and
furans from spiked and real contaminated soil. According to these experiments,
the extraction result mainly depends on the soil type, extraction conditions, and
type of contaminant. Sand is usually the best matrix for extraction, whereas mud
is considered to be a difficult matrix. The success of the extraction operation
depends on the soil-pollutant interaction, which is difficult to predict because
there are so many types of soil. Contaminants which do not bind strongly to the
soil are therefore the extraction targets with the most potential. It should be
remembered that it is easier to extract pollutants from spiked soil than from real
contaminated soil.

The operating principle of the supercritical carbon dioxide extraction of soil is

described in Papers [p. 717] and [p. 219]. Furthermore, equipment for soil
remediation is presented in Paper [pp. 228231]. The extraction vessels are
usually operated batch-wise. The solids handling in high-capacity, high-pressure
batch processes is a notable disadvantage, and an efficient method of moving the
soil into the high-pressure extractor would be a significant advancement.

21
 3.6 Separations in continuously operated columns

Supercritical Fluid Chromatography (SFC) with pure carbon dioxide eluent is

applicable to the separation of relatively non-polar compounds, i.e. compounds
which are soluble in toluene, hexane, freons and chlorinated solvents. A
distinctive characteristic of SFC is that ion-ion interactions between eluted
compounds and silica are practically absent. For example, compounds which
contain primary or secondary amine groups are selectively fractionated with
SFC. These compounds are generally impossible to separate by HPLC-silica
systems due to severe peak tailing. The benefits of SFC are the increased
separation rates due to high molecular diffusion in supercritical fluids, low
operating costs because of low energy consumption in recycling pressurized
carbon dioxide, non-toxicity and non-flammability of the carbon dioxide eluent,
and simple recovery of products from the eluent by pressure reduction. An
industrial-scale supercritical fluid chromatography plant for the purification of
cyclosporin is presented by Aaltonen et al. [41].

A supercritical fluid can be applied as a separation agent in the same way as

other solvents are applied in other separation processes, such as continuous
countercurrent liquid-liquid extraction or gas absorption. Instead of using a
liquid solvent supercritical fluid is used as a solvent for separation. Because the
feed is liquid, it is possible to use the continuous mode of operation, which is
much more suitable for high-pressure processes than the semi-batch mode. A
two-cascade column containing a stripping and an enriching section can be
continuously operated with relative ease. The same kind of equipment is needed
to carry out continuous countercurrent supercritical fluid extraction, as in the
semi-batch system presented in Figure 2, except that the extraction vessel in
Figure 2 is replaced by a column in which the feed liquid is continuously
pumped. A continuously operated raffinate valve is also needed at the bottom of
the column, so that the liquid feed can be removed from the column, and the
phase boundary inside the column is kept constant. This valve can be operated
manually or automatically, for example by using an optical sensor to control the
phase boundary.

According to Brunner [42], a general field of applications for countercurrent

supercritical fluid extraction include fine chemicals such as free fatty acids,
tococromanols, carotinoids, squalane, squalene, iso-cyanides, lecithin,

22
glyserides, hydrocarbons, citrus oils, organic compounds from aqueous extracts,
and others.

The separation of organics from aqueous solutions by applying supercritical

extraction has been studied by several research groups. Applications include the
purification of industrial waste waters [43, 44], the separation of azeotropic
mixtures [45], the enrichment of flavor fractions from wine or juice [4649], and
the separation of organics from fermentation processes [50].

Tiegs et al. [51] have used countercurrent a packed extraction column equipped
with reflux to extract fatty acid ethyl esters from fish oil. Simes et al. [52]
reported mass transfer results for the separation of a mixture of two terpenes of
similar volatilities. Carmelo et al. [53] have designed a column for the extraction
of free fatty acids (FFA) from olive oil.

The extraction of alcohols, such as ethanol, propanol or phenol, from aqueous

solution has been tested intensively [5459]. The separation of acetic acid from a
dilute aqueous solution has been tried [1], but the distribution coefficient of
acetic acid in a CO2/acetic acid/water system is only about 0.03 (weight basis),
which means that this application is not technically feasible. A partial list of
other organics tested includes dioxane, acetone, formamide, N,N-dimethyl
formamide, and ethylene glycol [1]. One possibility is to utilize the acidic
property of carbon dioxide, and to use it as a solvent to extract weakly basic
organics like pyridine from an aqueous solution [60].

Several other potential applications have undergone development. These

applications include the regeneration of activated carbon, the swelling of
polymers, and the separation of hydrocarbon and oil mixtures [1].

23
 4. Solubility measurements
In the first paper of this thesis [I], the solubility of 6-caprolactam in supercritical
carbon dioxide was reported. The ability of dense carbon dioxide to dissolve 6-
caprolactam could possibly be utilized in the industry related to nylon
production. Carbon dioxide could be used as a solvent to separate 6-caprolactam
from various solid or liquid feeds in applications related to production, the
recycling of used nylon or the purification of waste streams containing 6-
caprolactam.

4.1 Experimental

The solubility of 6-caprolactam in supercritical carbon dioxide was measured in

the static view cell apparatus [I]. The apparatus is equipped with a sapphire
window, which allows visual observation of high-pressure phase behavior. A
schematic diagram of the apparatus used in the experiments is shown in Figure
3.

Solubility measurements were carried out by first charging a desired amount of

solid to the cell, after which the cell was slowly pressurized by pumping in
carbon dioxide. A carbon dioxide pump control unit was used to calculate the
amount of carbon dioxide pumped to the cell. The unit showed how much the
volume of the pump cylinder changed during the pressure vessel loading while
the piston was adjusted to maintain constant pressure. After loading, the pressure
in the closed cell was slowly increased by moving the piston inside the cell until
complete miscibility of the solid and the solvent was reached. After this, the
pressure was slowly reduced until a second phase appeared. These phase
changes were recorded on video tape for later examinations. The solubility of the
solid is calculated from the masses of the solid and carbon dioxide. Details of the
procedure have been reported in Paper I.

24
 N

TI PI
F E A
C
B

D
J
I
K L
G

H M

Figure 3. Apparatus used in solubility measurements.

A, variable volume view cell; B, Boroscope; C, camera; D, light source; E,

carbon dioxide pump; F, carbon dioxide container; G, hydraulic oil pump; H,
oil container; I, data acquisition and control unit; J, magnetic stirrer, K,
computer; L, monitor; M, pump control unit; N, air bath.

4.2. Solubility results

6-Caprolactam was found to exhibit relatively high solubility in supercritical
carbon dioxide, i.e. up to around 17 wt% in Figure 4. This was expected, since
6-caprolactam is very soluble in most common organic solvents [61]. The shape
of the isotherms was relatively similar at all three temperatures, and the
solubility curves increase steeply with pressure. The system temperature usually
has a significant effect on the solid solubility in supercritical fluids, because it
influences the solid vapor pressure, solvent density and solute-solvent
interactions. In these experiments the temperature range was relatively narrow,
and there were no significant temperature effects. The solubility was mostly
affected by the solvent density, as seen in Table 3.

25
 0.08

0.07

0.06

0.05
y

0.04

0.03

0.02

0.01
80 100 120 140 160 180 200 220 240
p, bar

Figure 4. Mole fraction solubility of 6-caprolactam in supercritical carbon

dioxide as a function of pressure: (
) 307 K; () 314 K; () 324 K; ()
calculated with PR-EOS [I].

26
Table 3. Mole fraction solubility of 6-caprolactam in supercritical carbon
dioxide [I, Table 2].

T = 307 K T = 314 K T = 324 K

p CO2 103 y p CO2 3
10 y p CO2 103 y
-3 -3
bar kg m - bar kg m - bar kg m-3 -
101 730.1 20.1 138 752.2 22.1 141 666.5 21.5
108 750.2 22.5 149 772.2 29.2 154 701.9 22.1
114 764.3 25.2 156 783.2 32.7 172 738.2 29.2
124 784.2 28.3 169 801.2 40.2 172 738.2 32.7
134 800.7 35.8 179 813.5 50.4 200 779.3 42.2
142 812.1 40.2 180 814.7 48.0 201 780.5 48.0
145 816.1 42.2 191 826.4 58.2 203 783.0 40.2
149 821.2 39.9 196 831.4 54.6 217 799.0 50.4
151 823.7 45.4 208 842.7 73.3 227 809.3 54.6
152 824.9 43.5
154 827.3 48.8
154 827.3 58.2
168 842.6 58.3
173 847.6 73.3

The Peng-Robinson equation of state was used to model the solubility of 6-

caprolactam into supercritical carbon dioxide. Two adjustable parameters were
fitted to the experimental data by the Simplex search method as described in
Paper I. The first parameter is a mixture parameter describing the intermolecular
interaction between the unlike molecules, and the second parameter stands for
the effect of the different size and structure of unlike components. No crossover
pressure, i.e. the pressure at which two isotherms intersect, was found under the
experimental conditions, although according to the Peng-Robinson model,
isotherms at 314 K and 324 K seem to cross at 130 bar. The Peng-Robinson
model with two adjustable parameters fitted to the experimental data relatively
well at lower pressures, whereas at high pressures there seemed to be a
deviation, especially at 307 K.

27
 5. Soil extraction measurements
Prior to the experimental work, a literature review concerning the removal of
organic pollutants from soil was written [II]. The primary purpose of the soil
extraction work was to study the extraction of selected pollutants from soil-water
slurries. The basic idea was to avoid the technically cumbersome semi-batch
extraction process by first slurrying the soil with water, and then continuously
pumping the soil-water slurry to the extractor, where the pollutants were
removed from the soil.

5.1 Experimental

The characterization and preparation of the soil samples as well as the extraction
apparatus and working procedures are briefly described in this section.

5.1.1 Soil characterization and preparation

EURO-soils 5 and 6 were chosen as standardized soils. These soils had been
dried in an air-conditioned laboratory for 3 to 4 months, sieved, homogenized,
and sterilized by radiation. They were received from the EEC Joint Research
Center (Ispra, Italy). Table 4 shows the main pedological parameters of the soils.

Table 4. Main pedological parameters of EURO-soils 5 and 6 [IV].

Pedological characterization EURO-soil 5 EURO-soil 6

Sand / % 81.5 1.7

Silt / % 12.5 82.3
Clay / % 6.0 16.0
pH in water 4.5 8.3
Organic carbon / % 9.23 0.25
Organic matter / % 15.92 0.78

28
The EURO-soil samples were spiked using the following procedure.
Approximately 300 g of EURO-soil was weighed and put into a 1000 ml flask.
Because the soil samples were completely dry, 810 wt-% water was first added
to the soils. The flask was then rotated in a rotavapor (Heidolph VV 2000) for at
least 12 hours, in order to homogenize the soil moisture. The soil was then
spiked with trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol
(Fluga AG, tech.) and phenanthrene (Fluka AG, purum). The desired amount of
these compounds were weighed and dissolved into 200 ml dichloromethane
(Fluga AG, purum). The mixture was decanted into the flask containing the soil.
The soil slurry was then rotated for at least 12 hours, after which
dichloromethane was evaporated slowly to dryness at room temperature. The
spiked soil was then kept in the fume hood for 24 hours to assure that there was
no dichromethane residue in the soil. Soil samples taken from contaminated soil
areas were not characterized.

5.1.2 Soil extraction apparatus and procedure

Extractions were performed using the laboratory-built extraction apparatus

presented in Figure 5. Compressed carbon dioxide flows through the extraction
vessel (100 ml) and through the spiked soil (typically 20 g). The vessel is heated
to the extraction temperature in the air bath. Carbon dioxide leaving the
extraction vessel and containing the dissolved solids is expanded in a cold trap.
A heated micrometering valve is used to regulate the carbon dioxide flow-rate
(50 g/h). The exhaust carbon dioxide is vented to the atmosphere after passing
through silica and activated carbon beds, a rotameter and a dry gas meter. The
pressure is controlled manually from the compressor (5 bar) and the
temperature is controlled by the air bath regulator (1 C).

The residual concentrations of polycyclic aromatic hydrocarbons (PAHs) and

chlorophenols in the soil were analyzed after each extraction. PAHs were
analyzed with a HP 5890 gas chromatograph (GC) equipped with a 30 m DB-
1301 fused silica (J&W) capillary column. The detector was a HP 5970 Mass
Selective Detector (MSD). The detection and quantification were performed in
SIM-mode (Electron Ionization). The chlorophenol analysis was performed with
a HP 5890 gas chromatograph equipped with Electron Capture Detectors (ECD)
and two columns, 30 m 0.25 mm ID coated with 0.25 m films of SPB-5 and

29
SPB-35 (Supelco). More details concerning the analytic procedure are given in
Paper [IV].

CO2
CONTAINER

Figure 5. Soil extraction apparatus.

5.2. Soil extraction results

In Papers III and IV the extraction studies were carried out using either
standardized soil, which was spiked with known amounts of pollutants before
extraction, or by using soil samples taken from contaminated soil areas
originally containing pollutants.

30
 5.2.1 Extraction from spiked soil

The effect of soil moisture content on the residual pollutant concentration in the
soil after extraction was the most important factor to be studied [IV]. The effect
of extraction pressure, temperature, pH, carbon dioxide mass-flow rate, and
extraction time on the residual pollutant concentration in the soil after extraction
was also studied systematically [III, IV]. The experimental parameters and
results are presented in Paper IV (Tables 3 and 4). Table 5 illustrates the best
results and the set of extraction parameters with which these results were
obtained.

Table 5. The best extraction results and parameters.

Pollutants: (1) phenanthrene, (2) 2,3,4,6-tetrachlorophenol, (3)

pentachlorophenol. T is the extraction temperature, p is the extraction pressure,
w is the soil moisture content, pH is the soil acidity, S is the carbon dioxide
solvent flow rate, t is the extraction time, Cf is the final pollutant concentration
in the soil after extraction, Ci is the initial pollutant concentration in the soil
before extraction.

Soil Pollutant T p w pH S t Cf Ci

(C) (bar) (wt%-H2O) (kg/h) (min) (mg/kg) (mg/kg)

5
1 64 295 7.2 4.5 1.4 20 81 1 760
2 64 295 7.2 4.5 1.4 20 101 1 870
3 64 295 7.2 4.5 1.4 20 43 550
6
1 50 200 7.9 5.9 3 45 35 2 490
2 64 295 14.0 6.7 1.5 20 8.5 940
3 64 295 14.0 6.7 1.5 20 6.8 510

The selected pollutants were phenanthrene, 2,3,4,6-tetrachlorophenol and

pentachlorophenol, and the selected soil matrices were standardized EURO-soils
5 and 6. According to Finnish recommendations [62], soil containing over 40
mg/kg phenanthrene, or over 4 mg/kg 2,3,4,6-tetrachlorophenol or pentachloro-

31
phenol is regarded as contaminated soil. In most extractions the final pollutant
concentrations in the soil after extraction were not below the recommended
values.

The initial water content in the soil tested in the experiments was 740 wt%. The
experiments were carried out at relatively low temperatures (2565 C), and the
extraction pressure range was 100300 bar. The soil pH was changed by adding
a weak aqueous solution of either H2SO4 or K2CO3 to the soil. By using a
relatively high solvent flow rate (0.63 kg/h), it was possible to keep the
extraction time relatively short (2045 min).

The effect of soil moisture content on the pollutant concentration in the soil after
extraction was dominant in all of the soil extraction experiments. Generally, the
extraction of pollutants from soil-water slurries was not successful. Yeo and
Akgerman [63] have affirmed this conclusion by extracting phenol and
naphthalene from soil-water slurries at 47 C and 175 bar. They were able to
extract only 15 % of the initial amount of naphthalene and 60% of the initial
amount of phenol from the soil.

It was found, that in order to reach the level of acceptable residual pollutant
concentrations in the soil, it was necessary to keep the soil moisture content
below approximately 10 wt%. It is possible that slurrying the soil with water
reinforces the adsorption between the soil and the hydrophobic pollutant, and the
extraction result weakens. According to Andrews [64], the addition of small
amounts of polar modifiers like water or methanol dramatically reduces PAH
adsorption, indicating competition for polar adsorption sites on the soil. The
highly polar aqueous environment deactivates the polar adsorption sites, leaving
weak inductive, dispersive, and hydrophobic interactions as the only mechanism
for sorption. However, non-ionic and nonpolar PAHs interact primarily with
organic soil matter. Due to the negligible solubility of PAHs in water, adsorption
onto the soil is highly favored in soil-water slurries [64]. It also seems
reasonable to assume that water forms an extra mass transfer barrier, filling the
soil pores, and carbon dioxide is not able to contact and dissolve the pollutant. A
third possibility is that carbon dioxide saturated with water is no longer a good
solvent for non-polar pollutants.

32
The effect of other parameters on the residual pollutant concentration in the soil
was moderate compared with the effect of soil moisture content, even though it
was noticed that the highest extraction pressure and temperature were favorable.
This result is obvious, because a higher extraction temperature typically
increases the pollutant desorption from the soil. Also, increasing the extraction
pressure raises the solvent density and therefore increases the solubility of the
pollutant in the supercritical carbon dioxide solvent.

It proved to be more difficult to remove 2,3,4,6-tetrachlorophenol and

pentachlorophenol from soil 5 than from soil 6. This is due to the fact that
EURO-soil 5 contains more organic matter than EURO-soil 6. Chlorophenols
tend to bind strongly to organic matter. Reducing the pollutant sorption onto
organic soil matter seems to be a key factor in soil extraction. One way to reduce
the pollutant sorption is to increase the extraction temperature. It should be noted
that increasing the extraction temperature, while keeping the pressure constant,
reduces the carbon dioxide density, which usually reduces the pollutant
solubility in the carbon dioxide. Therefore, the extraction pressure must be
increased simultaneously to enhance the extraction.

5.2.2 Extraction from contaminated soil

Polycyclic aromatic hydrocarbons (PAHs) and chlorophenols were extracted

from two different soil samples collected from polluted soil areas. In particular,
the effect of soil moisture content on extraction efficiency was studied.

Polycyclic aromatic hydrocarbons (PAHs) were extracted from railway yard soil
[IV]. The soil initially contained 50 mg/kg of PAHs. The soil was extracted with
supercritical carbon dioxide at 200 bar and 40 C. In the first experiment, the
soil moisture content was 10 wt%. In this case the residual concentration of
PAHs in the soil after extraction was 7 mg/kg. In the second experiment, the soil
was slurried in water, and the soil moisture content was 50 wt%. This
experiment was clearly worse. The residual concentration of PAHs in the soil
after extraction was 30 mg/kg. The concentration of PAHs in the soil as a
function of time is presented in Figure 6. Obviously, the presence of a relatively
large amount of water (50 wt%) did make the efficient extraction of PAHs from
the soil more difficult.

33
concentration in soil, mg/kg
100 moisture
50 wt%

50 initial moisture 9,8 wt%

final moisture 0,13 wt%
30

20

10

5
0 20 40 60 80 100 120 140
time, min

Figure 6. Extraction of PAHs from railway yard soil with supercritical carbon
dioxide at 200 bar and 40 C.

Chlorophenols were extracted from sawmill soil [IV]. The soil contained
initially 62 mg/kg of 2,4,6-trichlorophenol, 3440 mg/kg of 2,3,4,6-
tetrachlorophenol, and 800 mg/kg of pentachlorophenol. In the first experiment,
the soil moisture content was 10 wt%. In this case the residual concentrations of
the three chlorophenols in the soil after extraction were 0.5 mg/kg for 2,4,6-
trichlorophenol, 23 mg/kg for 2,3,4,6-tetrachlorophenol, and 24 mg/kg for
pentachlorophenol. The concentration of 2,4,6-trichlorophenol in the soil as a
function of extraction time is presented in Figure 7.

34
 Concentration in soil, mg/kg recovery-%
100 99,5 recovery
50
99 concentration
20
10 98,5
5
2 98
1
97,5
0,5
0,2 97
0 20 40 60 80 100 120 140
time, min

Figure 7. Extraction of 2,4,6-trichlorophenol from saw mill soil with

supercritical carbon dioxide at 200 bar and 40 C. Moisture content 10 wt%.

In the second experiment, the soil was slurried in water, and the soil moisture
content was 50 wt%. As in the case of the extraction of PAHs from the railway
yard soil, the second experiment was worse. The residual concentrations of the
three chlorophenols in the soil after extraction were 3.1 mg/kg, 320 mg/kg, and
230 mg/kg, respectively.

35
 6. Continuous column extractions
In Papers V, VI and VII a mechanically agitated high-pressure column was
designed and tested by extracting organic compounds from aqueous solutions
using dense carbon dioxide as a solvent. In Paper V a mechanically agitated
continuous countercurrent rotating disk extraction column (RDC) was
introduced by extracting ethanol from an aqueous solution. In Paper VI an
Oldshue-Rushton type column was tested in the same application. In Paper VII
the extraction of 1-butanol from an aqueous solution was studied using
supercritical carbon dioxide solvent in an Oldshue-Rushton column.

6.1 Experimental

The equipment, working procedures and calculation methods that were used in
Papers VVII are presented in this section.

6.1.1. Equipment

A schematic view of the bench-scale experimental apparatus used in the

experiments [V, VI, VII] is presented in Figure 8. The extraction column
(Chematur Ecoplanning Co.) has a 35 mm internal diameter, is 2 m in height,
and can be used up to 40 MPa. A special pressure compensating sealing system
was developed to lead the electrically driven agitator shaft through the column
head. The maximum rotating speed in this construction is around 400 rpm. The
windows in the middle and at both ends of the column allowed observation of
the liquid level and fluid hydraulics. The column is equipped with a heating
jacket, in which water is circulated by a thermostat (Lauda C6 CS).

36
 Figure 8. Column extraction installation.

The column's internal design consists of removable parts that allow the use of
different agitator geometries or even different types of columns. The
characteristics of the RDC- and Oldshue-Rushton columns which were used in
the experiments [V, VI, VII] are summarized in Table 6.
Table 6. Rotating disk and Oldshue-Rushton column characteristics.
Character RDC Oldshue-Rushton
Height of the column, mm 2 000 2 000
Total agitated height of the column, mm 1 400 1 400
Column diameter, mm 35 35
Compartment height, mm 20 20
Stator plate opening diameter, mm 24 24
Smallest cross-sectional area, mm2 452 452
Number of compartments 99 99
Impeller or disk diameter, mm 20 20
Impeller or disk height, mm 4 1
Number of flat blades 4 -

37
A commercial high-pressure extraction unit (Nova Werke AG) was used to feed
carbon dioxide to the column. Carbon dioxide flow-rates were measured by two
high-pressure turbine flow meters (EG&G Flow Technology) in the solvent and
extract streams. No dispersers or other similar devices were used to create the
drops. The liquid feed stream was pumped to the top of the column by a high-
pressure piston pump (Lewa AG). The liquid feed and carbon dioxide solvent
streams were preheated to the extraction temperature by means of constant
temperature water baths.

The optical sensor (SITECSieber Engineering AG) controlling the interface

was focused on the phase boundary seen through the window at the top of the
column. The sensor sends signals to the control unit, which pneumatically opens
the needle valve placed in the raffinate stream. An alternative method of
controlling the interface is to use a manually operated needle valve placed in the
raffinate stream. The carbon dioxide flow rate was controlled by a
micrometering valve placed in the extract stream. This valve was operated
manually. The pressure inside the column was regulated by an automatically
controlled micrometering valve placed in the carbon dioxide solvent stream.

6.1.2 Column extraction procedure

An aqueous solution containing ethanol [V, VI] or 1-butanol [VII] was used as a
continuous phase and carbon dioxide as a dispersed phase in all of the
experiments. Prior to each run, the column was heated to the operating
temperature. The system was then pressurized to approximately 50 bars with
carbon dioxide, after which the aqueous solution was pumped to the top of the
column until the phase boundary was seen in the window at the top of the
column. The carbon dioxide compressor (Nova AG) was then turned on, the
system was pressurized to the extraction pressure, and the extract stream valve
was opened to let carbon dioxide flow through the continuous liquid phase. The
feed pump was then turned on again and the optical sensor controlling the liquid
level was activated. A tachometer was used to measure the speed of the rotor.

All of the experiments were carried out at 100 bar and 40 C. Each extraction
experiment lasted approximately 4 hours. Fresh carbon dioxide from the
container was used in all of the experiments to avoid using a preloaded solvent.
During the run the feed and raffinate tanks were weighed, and the carbon

38
dioxide flow rates were measured every 20 minutes. After running for 2 hours,
the samples were taken from the feed, raffinate and extract streams once every
20 minutes. The extract from the separator was continuously collected. The
ethanol concentration in all of the samples was analyzed by GC. More details
concerning the sampling and material balance deviation are presented in the
Papers V, VI and VII.

The method described by Rathkamp et al. [59] was used to measure the
dispersed phase holdup. The data was obtained by shutting the feed pump and
carbon dioxide compressor off at steady state conditions, and measuring the
time required for the carbon dioxide drops that entered the bottom of the column
to rise to the top of the column. This information combined with the flow rate of
the dispersed phase was used to calculate the volume of the dispersed phase in
the column, and the holdup for the run was calculated. The raising drops were
recorded at various flow rates and rotor speeds by a video-camera looking
through the window in the middle of the column. The average diameter of the
drop was calculated for each experiment from a video freeze-frame.

It was not possible to measure flooding points with the optical sensor
construction, because the optical sensor opened the raffinate stream valve at the
bottom of the column when the liquid level started to rise. However, when the
solvent and feed flow rates reached certain values, the raffinate stream valve was
opento such an extent that most of the solvent flow came out of the column with
the raffinate stream. At this point the column was no longer operable. This point
was used to describe the capacity of the column.

6.1.3 Calculation of column efficiency

Because both RDC- and Oldshue-Rushton columns are continuously operating

columns, the HTU/NTU concept was used to estimate the column efficiency and
to calculate the mass transfer coefficients. According to the two-film theory, the
resistance in the solvent phase controls the mass transfer, provided that the
distribution coefficient is relatively small [65]. Therefore the calculation was
based on the dispersed carbon dioxide phase. For dilute solutions, an immiscible
solvent and a linear equilibrium line, the number of transfer units (NTUod), the
height of a transfer unit (HTUod), and the overall mass transfer coefficient Kod
for the dispersed phase can be written as

39
 y1
dy
NTU od = (1)
y2
y y *

Z
HTU od = (2)
NTU od

Vd
Kod a = (3)
HTU od

where y is the weight fraction of solute in the dispersed phase, y* is the

equilibrium value, Vd is the superficial velocity of the dispersed phase, and a is
the interfacial area. The concentration of solute in the extract stream was
calculated by the overall material balance, and this value was used when Koda-
and HETS -values were calculated.

According to Treybal [65] the relationship between the height equivalent to a

theoretical stage (HETS) and the height of a transfer unit (HTUod) is given by

ln E
HETS = HTU od (4)
E 1

where E is the extraction coefficient._ The slip velocity through the smallest
cross-sectional area of the column Vs describes the relative velocity of the
phases, and is defined as

_ _
_ V V
Vs = d + c (5)
h 1 h

40
 _ _
where Vd and Vc are the relative velocities of the dispersed and continuous
phases through the smallest cross-sectional area, and h is the dispersed phase
holdup.

6.2 Column extraction results

6.2.1 Column efficiency

In Table 7 the values of the overall mass transfer coefficient Koda and the height
equivalent to a theoretical stage HETS are compiled [V, VI, VII]. The extraction
efficiencies in RDC- and Oldshue-Rushton columns are relatively similar to
each other. The measured Koda values for the extraction of ethanol from water in
the RDC-column range from 0.006 s-1 to 0.015 s-1, and in the Oldshue-Rushton
column the values range from 0.009 s-1 to 0.012 s-1. The measured HETS values
are between 0.8 m and 0.37 m. Slightly lower Koda values were measured for 1-
butanol extraction than in ethanol extraction. In the case of 1-butanol extraction,
the measured Koda values are 0.0020.003 s-1, and the HETS values are 0.40.5
m in the Oldshue-Rushton column.

In the literature the values of the overall mass transfer coefficient Koda measured
for spray and packed continuous countercurrent supercritical fluid extraction
columns generally range from 0.006 s-1 to 0.04 s-1, depending on the type of
column, packing and solvent-to-feed ratio [57, 59]. Values of the height
equivalent to a theoretical stage HETS for small-scale spray, packed and sieve
tray supercritical fluid extraction columns have been measured by other authors
[54, 56, 57, 59]. The reported HETS values for the supercritical spray, packed
and sieve tray columns are typically in the range of 0.20.5 m.

It can be concluded that the Koda and HETS values measured in Papers V,VI and
VII for the RDC- and Oldshue-Rushton columns are of the same order of
magnitude as those presented for small-scale supercritical spray and packed
columns in the literature.

41
Table 7. Mass transfer efficiencies in mechanically agitated columns [V, VI, VII].

No. S/F Rotor speed Concen- Concentration Concentration Koda HETS

(rpm) tration in in the raffinate in the extract (s-1103) (m)
the feed stream (wt%)
stream (wt%)
(wt%)

Extraction of ethanol in the RDC-column

1 13/1 0 10 2.59 78 6.0 0.80

2 50 2.17 82 7.2 0.67
3 158 0.97 84 9.7 0.46
4 223 0.78 86 12.7 0.37
5 301 0.84 80 11.1 0.41
6 388 0.95 81 10.3 0.44
7 13/1.5 0 10 2.30 84 13.0 0.44
8 104 2.69 91 12.3 0.49
9 207 2.75 89 11.0 0.53
10 312 2.52 89 11.8 0.49
11 13/2 0 10 3.76 89 11.6 0.58
12 103 3.39 89 13.0 0.50
13 204 3.70 89 13.1 0.52
14 303 3.32 84 14.8 0.45

Extraction of ethanol in the Oldshue-Rushton column

1 14/1 0 10 1.27 90 8.7 0.55

2 45 1.15 85 9.8 0.50
3 120 0.87 87 10.9 0.44
4 227 0.92 91 10.6 0.45
5 324 1.03 86 10.0 0.48
6 14/1.5 0 10 2.47 84 11.5 0.53
7 100 2.55 82 11.9 0.52
8 199 2.56 85 11.0 0.55
9 303 2.56 86 11.3 0.54
10 14/2 0 10 4.00 90 9.7 0.72
11 103 4.13 91 10.6 0.68
12 201 4.19 86 9.8 0.74
13 311 3.98 90 10.3 0.69

42
 Extraction of 1-butanol in the Oldshue-Rushton column

1 4.3/6 0 5 0.65 90 3.3 0.46

2 72 0.70 89 3.2 0.48
3 138 0.63 85 3.2 0.47
4 238 0.66 88 3.1 0.50
5 5.2/4.5 0 5 0.24 79 2.8 0.52
6 75 0.23 89 2.9 0.49
7 142 0.16 89 3.4 0.42
8 232 0.23 90 3.2 0.46
9 5.3/2 0 5 0.020 80 1.9 0.46
10 75 0.015 84 2.1 0.44
11 145 0.021 85 1.9 0.46
12 210 0.014 86 2.2 0.41

Mechanical agitation enhanced the column efficiency only at relatively high

solvent-to-feed ratios. At solvent-to-feed ratio S/F = 13, mechanical agitation
increased the Koda value from 0.006 s-1 to 0.013 s-1, and reduced the HETS
value from 0.8 m to 0.37 m for the RDC -column. On the other hand, agitation
did not enhance the extraction at lower solvent-to-feed ratios. The same kind of
behavior was noticed when the Oldshue-Rushton column was tested at solvent-
to-feed ratio S/F = 14. Mechanical agitation slightly increased the Koda value
from 0.009 s-1 to 0.011 s-1, and reduced the HETS value from 0.55 m to 0.44 m
in the case of the Oldshue-Rushton column. Mechanical agitation did not
enhance the column efficiency when 1-butanol was extracted from water,
presumably because the solvent-to-feed ratios used in this application were
relatively low, i.e. S/F = 0.92.7.

43
The effect of agitation on the values of the overall mass transfer coefficient Koda
and the height equivalent to a theoretical stage HETS at the highest experimental
solvent-to-feed ratios are presented in Figures 9 and 10.

0.02

0.015
Koda (1/s)

0.01

0.005

0
0 100 200 300 400 500
rotor speed (rpm )

Figure 9. Effect of agitation on Koda [V,VI,VII].

(
) extraction of 1-butanol in Oldshue-Rushton column, S/F= 4.3/6;

() extraction of ethanol in Oldshue-Rushton column, S/F=14/1;
() extraction of ethanol in RDC -column, S/F=13/1.

44
 1

0.9

0.8
HETS (m)

0.7

0.6

0.5

0.4

0.3
0 100 200 300 400 500
rotor speed (rpm )

Figure 10. Effect of agitation on HETS [V,VI,VII].

(
) extraction of 1-butanol in Oldshue-Rushton column, S/F= 4.3/6;

() extraction of ethanol in Oldshue-Rushton column, S/F=14/1;
() extraction of ethanol in RDC -column, S/F=13/1.

An efficiency optimum is seen in Figures 9 and 10 when ethanol is extracted at

solvent-to-feed ratios S/F = 13 and S/F = 14. The optimum rotor speed is
approximately 200 rpm. The same kind of behavior is known to occur in
conventional liquid-liquid RDC -columns. According to Robbins and Cusack
[66], the value of HETS becomes smaller with increased rotor speed but passes
through a minimum. Obviously, mechanical agitation reduces the dispersed
phase drop size and increases the dispersed phase holdup and interfacial area for
mass transfer. In addition, higher rotor speeds increase the axial mixing of each
phase. The two main factors of the axial mixing process are eddy diffusion or
backmixing, which is most pronounced at the highest speeds, and channeling,
which is specific in the forward direction [67]. Axial mixing, when present in
both phases, causes a reduction in the concentration driving force between the
phases. Therefore, the increased mass transfer rate caused by high rotor speed is

45
offset by increased axial mixing, resulting in an optimum rotor speed for each
operating condition.
Mechanical agitation seems to have an effect on column efficiency only at
relatively high solvent-to-feed ratios, e.g. S/F = 13 or S/F = 14. One possible
explanation is that at relatively low solvent-to-feed ratios, equilibrium is
approached in the column and mechanical agitation can no longer enhance the
extraction.
6.2.2 Column capacity
The total throughput of the RDC- and Oldshue-Rushton columns calculated as
the volumetric feed plus solvent flow rate divided by the smallest cross-sectional
area of the column is presented in Figure 11. The total throughput of the RDC-
column was approximately 80 m3 h-1 m-2 without agitation. Agitation slightly
lowered the value to 74 m3 h-1 m-2 when the rotor speed was 300 rpm. Without
agitation the total throughput of the Oldshue-Rushton column was
approximately 70 m3 h-1 m-2, whereas at 300 rpm the total throughput was
approximately 50 m3 h-1 m-2.
100

90
total throughput (m/h m)

80

70

60

50

40

30
0 50 100 150 200 250 300 350
rotor speed (rpm )

Figure 11. Effect of agitation on column capacity at 40 C and 100 bar. ()
Oldshue-Rushton column; () RDC -column.

46
Without agitation the capacities of the RDC- and Oldshue-Rushton columns are
relatively similar. The relative deviation of the values is approximately 12 %. At
300 rpm the capacity of the RDC -column is almost the same as without
agitation, whereas the capacity of the Oldshue-Rushton column is reduced
significantly at 300 rpm. One possible explanation is that the Oldshue-Rushton
type impeller provided more intense agitation than the relatively small-diameter
RDC -disk. When the agitation power input is increased, the drop diameter
decreases, and consequently the slip velocity and the column capacity decrease
as well. At relatively low power inputs this effect is rather small, but at higher
power inputs the drop size reduction reaches the point at which it becomes so
large that the slip velocity and the capacity are substantially reduced.

The capacity of mechanically agitated supercritical extraction columns is

significantly higher than that of the packed supercritical fluid extraction column,
and is approximately equal to the capacity of a supercritical spray column.
Flooding velocities for a 25.4 mm diameter column spray and packed column
operated under supercritical conditions for a carbon dioxide/2-propanol/water
system have been measured by Rathkamp et al. [59]. According to the authors,
the packed column flooded when the superficial velocity of the continuous phase
was Vc = 0.4 mm/s and the superficial velocity of the dispersed phase was Vd =
3.0 mm/s, whereas the spray column reached flooding at Vc = 0.4 mm/s and Vd =
20.3 mm/s. In this work, the capacity of the Oldshue-Rushton column without
agitation was approximately Vc = 5.0 mm/s and Vd = 14.0 mm/s, and at 150 rpm,
the capacity was approximately Vc = 4.9 mm/s and Vd = 11.6 mm/s. The RDC -
column was operable at approximately Vc = 5.3 mm/s and Vd = 15.6 mm/s.

Compared with conventional extraction systems, the capacity of continuous

countercurrent supercritical fluid extraction columns is higher most probably due
to the larger density difference of the phases in supercritical fluid extraction. For
example, the toluene/water system flooded in the mechanically agitated (200
rpm) Oldshue-Rushton column at approximately Vc = 5.0 mm/s and Vd = 4.5
mm/s [68].

The dispersed phase holdup and slip velocities were also measured in the RDC-
and Oldshue-Rushton columns. The results are presented in Table 8.

47
Table 8. Dispersed phase holdup and slip velocities in the RDC- and Oldshue-
Rushton columns.

S/F Speed of agitation Holdup Slip velocity

(rpm) (mm/s)
RDC -column
3.2/1.6 0 0.026 0.136
150 0.035 0.101
300 0.038 0.093
12/1.6 0 0.089 0.138
150 0.123 0.098
300 0.132 0.09
16/1.6 0 0.122 0.134
150 0.153 0.11
300 0.21 0.078
Oldshue-Rushton column
14/2 0 0.126 0.113
150 0.145 0.098
300 0.160 0.09
14/1.5 0 0.117 0.123
150 0.133 0.107
300 0.143 0.01
14/1 0 0.120 0.119
150 0.130 0.110
300 0.133 0.107

The measured dispersed phase holdup values are in the 0.030.20 range. As
expected, all of the holdup values increase with increasing rotor speed. All of the
slip velocity values decrease with increasing rotor speed because of increasing
holdup.

48
 7. Concluding remarks
Considering that there is a common need among chemical engineers to find
environmentally benign solvents, the use of relatively inexpensive carbon
dioxide solvent should increase in the future, provided that carbon dioxide
proves to be a technically feasible and economically competitive solvent in
selected industrial applications. In this thesis, the extraction of organic
compounds from solid and liquid matrices using supercritical carbon dioxide as
a solvent was studied.

Dense carbon dioxide is a very good solvent for the cyclic amide, 6-caprolactam,
and can be used to dissolve and extract it from solid and liquid matrices. The
ability of dense carbon dioxide to dissolve 6-caprolactam could possibly be
utilized in the industry producing nylon.

Certain criteria must be fulfilled before solvent extraction can be considered for
soil remediation [69]. The first criterion is that the process must be capable of
yielding uncontaminated residual material. The results of this thesis indicate that
at least 80-90 % of the initial amount of pollutant can be removed at moderate
temperatures even in the most difficult cases, and in many cases over 99 % of
the initial amount of pollutant can be removed from soil. Supercritical extraction
is best suited to sand or silt type soils, which have a low adsorption capacity.
The extraction results are found to be case-dependent and soil remediation at
moderate temperatures is observed to be difficult if the pollutant binds strongly
to the soil or if the acceptable level of residual concentration is very low. To
verify technical feasibility, a commercial-scale extraction system will have to be
successfully operated over an extended period. Only one such system is reported
to have been installed in Port Arthur, Texas [69]. Generally, there is plenty of
evidence in industry, e.g. the extraction of caffeine from coffee beans, that high-
pressure extraction is a viable technology. The solids handling in high-capacity,
high-pressure batch processes is a notable disadvantage, and an efficient method
of moving the soil into the high-pressure extractor would be a significant
advancement.

In this thesis a novel mechanically agitated countercurrent continuous extraction

column was introduced and tested by extracting ethanol and 1-butanol from
aqueous solutions in the rotating disk column and in the Oldshue-Rushton

49
column. A special pressure-compensating sealing system was used to lead the
electrically driven agitator shaft through the column head. The capacity of a
mechanically agitated supercritical extraction column is typically higher than
that of a conventional liquid-liquid extraction column due to the fact that the
density difference of the phases in supercritical extraction columns is larger than
in conventional extraction processes. A mechanically agitated column
successfully combines the high capacity of supercritical spray extraction
columns and the high efficiency of packed supercritical extraction columns.

The extraction of ethanol from water is technically not a very feasible

application due to the low distribution coefficient of ethanol in the carbon
dioxide/ethanol/water system. The extraction of high molecular weight alcohols
like 1-butanol from water is much more feasible than the extraction of ethanol,
because in this case the distribution coefficients are higher than in case of
ethanol extraction. Other potential applications include the extraction of
phenolics or pyridine from water, and all industrial separations in which the feed
is viscous or the extraction is mass transfer limited, and effective agitation is
needed.

50
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Published by Series title, number and
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Author(s)
Laitinen, Antero
Title
Supercritical fluid extraction of organic compounds
from solids and aqueous solutions
Abstract
In this thesis, the extraction of organic compounds from solid and liquid matrices using supercritical carbon
dioxide as a solvent was studied.
Dense carbon dioxide is a very good solvent for the cyclic amide, 6-caprolactam. 6-caprolactam exhibits
relatively high solubilities, i.e. up to around 17 wt% at ambient temperatures, and at pressures below 220
bar. Carbon dioxide can be used to dissolve and extract 6-caprolactam from solid and liquid matrices.
The remediation of contaminated soil by carbon dioxide extraction was studied. The effect of extraction
pressure, temperature, soil moisture content, pH, carbon dioxide mass flow rate, and extraction time on the
residual pollutant concentration in the soil after extraction was systematically studied. The selected
pollutants were phenanthrene, 2,3,4,6-tetrachlorophenol and pentachlorophenol. The results indicate that at
least 8090 % of the initial amount of pollutant can be removed at moderate temperatures even in the most
difficult cases, and in many cases over 99 % of the initial amount of pollutant can be removed from the
soil. Supercritical extraction is best suited to sand or silt type soils, which have a low adsorption capacity.
The extraction results are found to be case-dependent, and soil remediation at moderate temperatures is
observed to be difficult if the pollutant binds strongly to the soil or if the acceptable level of residual
concentration is very low.
A novel mechanically agitated countercurrent continuous extraction column was introduced by extracting
ethanol and 1-butanol from aqueous solutions in the rotating disk column and in the Oldshue-Rushton
column. Column efficiencies were measured as a function of solvent-to-feed ratio and rotor speed.
Generally, the values of the height equivalent to a theoretical stage HETS were in the range of 0.4-0.8 m.
Mechanical agitation enhanced the extraction only at relatively high solvent-to-feed ratios. Column
capacities for both types of column were measured, and the total throughput calculated as the feed plus
solvent flow rate divided by the smallest cross-sectional area was 50-80 m3h-1m-2. A mechanically
agitated column successfully combines the high capacity of supercritical spray columns and the high
efficiency of supercritical packed columns.

Keywords
organic compounds, extraction, solids, aqueous solutions, supercritical gases, supercritical fluids, carbon
dioxide, amides, lactams, solubility
Activity unit
VTT Chemical Technology, Process Technology, Biologinkuja 7, P.O.Box 1401, FIN02044 VTT, Finland
ISBN Project number
9513855511 (soft back ed.) K9SU00433
951385552-X (URL: http://www.inf.vtt.fi/pdf/
Date Language Pages Price
December 1999 English 58 p. + app. 84 p. C
Name of project Commissioned by
National Technology Agency (Tekes)
Series title and ISSN Sold by
VTT Publications VTT Information Service
12350621 (soft back ed.) P.O.Box 2000, FIN02044 VTT, Finland
14550849 (URL: http://www.inf.vtt.fi/pdf/) Phone internat. +358 9 456 4404
Fax +358 9 456 4374